Oxidized cellulose smoking product

ABSTRACT

Smoking products and process for their production wherein organic salts of potassium, lithium and copper, and titanium dioxide are incorporated into oxidized cellulosic materials for the purpose of controlling burning and for supporting glow between puffs. The potassium, lithium and copper organic acid salts employed are those of oxalic, lactic, glycolic, diglycolic, pivalic and tannic acid and in amounts less than 2 percent by weight.

United States Patent- [72] Inventors Theodore S. Briskin;

Geoffrey R. Ward, both of Beverly Hills, Calif.

Aug. 18, 1969 Oct. 12, 1971 Sutton Research Corporation Los Angeles,Calif.

Continuation-impart of application Ser. No. 802,229, Feb. 25, 1969,which is a continuation-in-part of application Ser. No. 595,622, Nov.21, 1966, now Patent No. 3,447,539, and a continuation-in-part of674,994, Oct. 12, 1967, now abandoned.

[21 Appl. No. [22] Filed [45] Patented [73] Assignee 54] OXlDlZEDCELLULOSE SMOKING PRODUCT 3 Claims, No Drawings [52] 11.8. CI 131/2 [5l] Int. Cl ..A24b 15/00, A24d 01/ 1 8 Primary Examiner-Melvin D. ReinAttorney-McDougall, Hersh, Scott & Ladd ABSTRACT: Smoking products andprocess for their production wherein organic salts of potassium, lithiumand copper, and titanium dioxide are incorporated into oxidizedcellulosic materials for the purpose of controlling burning and forsupporting glow between puffs. The potassium, lithium and copper organicacid salts employed are those of oxalic, lactic, glycolic, diglycolic,pivalic and tannic acid and in amounts less than 2 percent by weight.

OXIDIZED CELLULOSESMOKING PRODUCT This is a continuation-in-part of Ser.No. 802,229, filed Feb. 25, 1969, entitled Smoking Products which inturn is a continuation-in-part of Ser. No. 595,622, filed Nov. 21,.1966, now U.S. Pat. No. 3,447,539, and continuation-in-part of Ser. No.674,994, filed Oct. 12, 1967, now abandoned.

This invention relates to new smoking products.

As used herein, the term smoking products" is meant to refer to and toinclude filler material embodied in cigarettes, cigars and for use withpipes and the like, and mixtures thereof with various proportions oftobacco and including cigarette papers and wrappers used in thepreparation of such cigars and cigarettes, and it includes cigarettes,cigars and the like products manufactured with such filler materials andwrappers.

In the aforementioned applications, description is made ofthepreparation of a smoking product suitable for use in cigarettes, cigarsor with pipes wherein the smoking product is prepared of relatively purecellulosic materials subjected to selective oxidation with liquidnitrogen dioxide to convert preferably more than 90 percent of themethylol groups in the cellulosic molecule to yield a product which canbe referred to as an oxycellulose or polyuronic acid. The oxidationreaction product is further processed by removal of liquid nitrogendioxide by vaporization and preferably by washing the oxidizedcellulosic product with water and/or alcohol and/or acetone or othersolvent for removal of solubilized foreign material, including oils,waxes, latices and the like, which contribute undesirably to the tasteandaroma when used as a smoking product in accordance with the practiceof this invention. Y

One method for effecting this oxidationis disclosed in copendingapplication Ser. No. 745,221, filed July 16, 1968, now U.S. Pat. No.3,516,416, wherein description is made of the oxidation of a cellulosicmaterial by suspension in liquid,

nitrogen dioxide in the ratio of lpart by weight cellulosic material 5to 1000 parts by weight cellulosic material to 25 to 50 parts by weightof the liquid nitrogen dioxide. The reaction therein is carried out at atemperature within the range of to 65 C., and at auto genous pressurewhen the reaction temperature exceeds 21 C., the boiling point ofnitrogen dioxide.

Another method for effecting this oxidation is disclosed in copendingapplication Ser. No. 745,135, entitled Preparation of Smoking Productsof Cellulose Derivatives and Process," filed July 16, 1968, now U.S.Pat. No. 3,491,766, wherein the oxidation reaction, including reactionrate and amount of conversion, is materially improved by formulation ofthe oxidation reaction mixture to contain up to 8 percent by weight ofwater in the liquid nitrogen dioxide system and by carrying out thereaction at elevated temperatures about 15 C., and preferably betweenthe range of to 45C., depending somewhat upon the amount of moisturepresent in the reaction medium, whereby the reaction medium is renderedrelatively nonelectrically conductive so that the presence of water inthe reaction medium will not result in attack or degradation of thecellulosic material to be oxidized, and wherein the formulation toinclude aqueous medium in the reaction of liquid nitrogen dioxide alsooperates to adjust the specific gravity of the reaction mixture in thedirection towards the specific gravity of the cellulosic materialwhereby suspension of the cellulosic material in the reaction medium iseasier to achieve and maintain. The result is a more rapid and uniformoxidation reaction of the cellulosic material to produce a betterproduct at a more rapid rate.

A further method for effecting the oxidation of cellulosic materials isdisclosed in copending application Ser. No. 774,064, filed Nov. 7, I968,and entitled Method for Producing Smoking Product of Oxidized CellulosicMaterial" wherein the cellulosic material is first wetted with liquidnitrogen dioxide and then is exposed to hot gaseous nitrogen dioxide.This particular method can be advantageously used in the form of acontinuous process for the production of large quantities of oxidizedcellulosic materials.

The resulting smoking product is then formulated with mineralizingagents such as oxalates, glycolates, diglycolates, lactates, pivalatesor tannates of such metals as calcium, magnesium, lithium, potassium,barium, strontium, preferably introduced to form the salt internally inthe cellulosic derivative for purposes of providing desired ashingcharacteristics. Instead of forming the described salts internally inthe cellulosic derivative, limited beneficial characteristicscan beachieved by external application of such mineralizing agents. Asdescribed, the desired internal introduction is achieved by firstwetting the cellulosic derivative with metal cation in dilute solutionfor absorption into the cellulosic derivative followed by exposure to.the acid anion in solution to precipitate the metal salt in situ in thecellulosic material.

This application is addressed to a process for the treatment of oxidizedcellulosic material, independent of the method by which the cellulosicmaterial is oxidized with an organic salt of potassium, lithiumorcopper, or titanium dioxide to improve the burning characteristics ofoxidized cellulosic material.

It is an object of the present invention to produce and to provide amethod for producing a cellulosic material which is suitable for use insmoking and which finds wide acceptance as a smoking product from thestandpoint of taste, aroma, appearance, burning characteristics andrelative absence of undesirable reaction products.

As the cellulosic raw materials, use can be made of various forms ofcellulose, such as wood pulp, straw, alpha-cellulose, flax, fibrouscarbohydrates, seaweed carbohydrates, bamboo filaments, cottonfilaments, hemp, refined paper, rice paper, filamentous gums and evenplants and plant leaves and the like fibrous materials from whichnoncarbohydrate components have been separated, all of which ishereinafter referred to as cellulosic material.

It is preferred to make use of a purified cellulosic material from whichvarious of the sugars, proteins, chlorophylls, flavones, colors,lignins, oils, waxes, resins and lactices have been removed since thesecontribute undesirable odors and tastes to the smoking product.

It is known that various additives may be included in smoking productsto insure proper burning and glow sustenance. However, in priorcompositions potassium nitrate has been the primary additive in spite ofthe fact that the nitrate may be converted by polyanhydroglucuronic acidto the potassium salt with the liberation and loss of nitric acid.

In accordance with the present invention, oxidized cellulosic materialis treated with a burning control agent which is believed to have acatalytic effect upon the burning of oxidized cellulose. The catalyticeffect not only provides for glow sustenance and control of the rate ofburning, but also serves to promote more complete combustion of theoxidized cellulose to carbon monoxide, carbon dioxide and water.

It has been found that organic salts of potassium, lithium and copper,as well as titanium dioxide exhibit this catalytic effect. While theoxalate is the preferred salt, use may also be made of the lactate,glycolate, diglycolate, pivalate and tannate salts.

The treatment of the oxidized cellulosic materials is such that theburning control agent is incorporated into or associated with thecellulose. ln referring to incorporation" or assocation,"it will beunderstood that no specific limitation is intended. Diffusion within thefibers of the material being treated has been recognized, while presenceof the material in particulate form on' the exterior of the fibers isalso contemplated.

It is generally sufiicient to add the burning control agent in an amountcorresponding to up to 2 percent by weight upon the oxidized cellulosicmaterial. An amount in the range of 0.001 to 1 percent is preferred.

The burning control agents may be incorporated into the oxidizedcellulosic material in a wide variety of ways. ln the case of the metalsalts, it is possible to treat the oxidized cellulose with an aqueous oran aqueous alcoholic solution of the burning control agent. Any otherinert solvent may also be used. Such solutions generally contain theburning control agent in an amount corresponding to 0.001 to percent byweight based upon the total weight of the solution. The oxidizedcellulose is preferably treated with the solution by spraying thesolution onto the cellulosic material in a conventional manner.

If desired, the cellulosic material may be washed after treatment toprovide for removal of excess salt.

In the case of titanium dioxide, it is preferred to admix the titaniumdioxide with the cellulosic material in dry form. The mixture is blendedto insure uniform distribution of the titanium dioxide throughout thecellulosic material.

The following examples illustrate a typical process for the preparationof a smoking product in accordance with the invention.

EXAMPLE! A highly purified commercial grade of wood pulp is fabricatedinto a thin paper of a thickness comparable to commercial cigarettepaper. This paper is shredded into strands of about 2 millimeters widthand immersed in approximately one hundred times its weight of liquidnitrogen dioxide maintained at 20 C. Immersion continues for about fiveto ten days, or until testing indicates a carboxyl level of 92 to 100percent expressed as polyanhydroglucuronic acid content. The testinginvolves washing in aqueous alcohol, drying, dissolving in ex cessstandard alkali, and then back titrating with standard acid.

The shredded material is freed of excess nitrogen dioxide by means of awarm stream of dry air. Thereafter, a 0.01 percent aqueous solution ofcopper oxalate is sprayed over the surface of the oxidized cellulose.After the spraying operation is completed, the oxidized cellulosicmaterials are allowed to dry whereby the water evaporates leaving copperoxalate in the cellulosic material. The amount of copper oxalate presentin the material constitutes about 0.001 percent by weight of thecellulosic material.

EXAMPLE [1 Oxidized cellulose prepared in the manner shown in example Iis admixed with powdered titanium dioxide, and the mixture blended toinsure uniform distribution of the titanium dioxide throughout thecellulosic material.

EXAMPLE Ill Oxidized cellulose prepared in the same manner shown inexample 1 is sprayed with a 0.01 percent aqueous solution of lithiumoxalate. The lithium oxalate constitutes a 0.0015 percent by weight ofthe cellulosic material.

The materials prepared in accordance with the practice of this inventionfind excellent use as a smoking product in cigarettes, pipes and likesmoking devices. Use can be made of the treated material alone or inadmixture, in various proportions with tobacco. A cigarette can be madeby cylindrically wrapping the shredded material with cigarette paper, orpreferably with paper treated in accordance with the instant invention,or better still with a paper made with pulp thus treated. A cigarettefilter can then be attached, such a filter being treated with anappropriate flavor such as menthol. lndividuals smoking the individualtype product will experience a clean taste, and the smoke inhaled willprove to be extremely mild, and in no sense irritating.

It will be understood that various changes and modifications may be madein the above-described products which provide the characteristics of theinvention without departing from the spirit thereof particularly asdefined in the following claims.

1. A smokable product comprising a charge of oxidized cellulosicmaterial and a compound selected from the group consisting of titaniumdioxide and an organic acid salt of a metal selected from the groupconsisting of copper, potassium and lithium, wherein said organic acidis selected from the group consisting of oxalic, lactic, glycolic,diglycolic, pivalic and tannic acids.

2. A smokable product as defined in claim 1 wherein said compound ispresent in an amount corresponding to 0.001 to 2 percent by weight.

3. A smokable product as defined in claim 1 which includes an ashingagent.

Disclaimer and Dedication 3,612,063.-The0dm"e S. Brislcin and GeojfweyR. Ward, Beverly Hills, Calif. OXIDIZED CELLULOSE SMOLING PRODUCT.Patent dated Oct. 12, 1971. Disclaimer and dedication filed Apr. 8,1971, by the assignee, Sutton Research Corporation. Hereby disclaims anddedicates to the Public the portion of the term of the patent subsequentto Feb. 2, 1988.

[Ofiicial Gazette April 18, 1972.]

2. A smokable product as defined in claim 1 wherein said compound ispresent in an amount corresponding to 0.001 to 2 percent by weight.
 3. Asmokable product as defined in claim 1 which includes an ashing agent.